CN113149116B - Porous ceramic membrane with high seawater desalination efficiency and self-cleaning function and preparation method thereof - Google Patents
Porous ceramic membrane with high seawater desalination efficiency and self-cleaning function and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
Abstract
The invention disclosesA porous ceramic membrane with high seawater desalting efficiency and self-cleaning function and its preparing process are disclosed, which features that its phase composition is TiB 2 +Ti(C,N)+Ti 3 Two-dimensional nano photothermal materials grow in or on the porous ceramic support pore structure of the SiC, or/and carbon nano materials are deposited on the surface of the porous ceramic support pore structure; the multi-stage heterogeneous porous ceramic membrane forms a three-dimensional communicated multi-stage porous structure with three apertures simultaneously through the self reaction of raw materials and an additional pore-forming agent. The multi-stage heterogeneous porous ceramic can enable an incident light path to generate diffuse reflection reaction due to the three-dimensional structure so as to improve the light absorption rate, and meanwhile, the two-dimensional photo-thermal material with narrow band gap energy and plasma resonance effect on the surface and the inside can further improve the light absorption rate of the material, so that the photo-thermal conversion efficiency is improved.
Description
Technical Field
The invention relates to the field of photo-thermal seawater desalination, in particular to preparation and application of a multi-stage heterogeneous porous ceramic membrane with high seawater desalination efficiency and a self-cleaning function.
The multi-stage heterogeneous porous ceramic membrane can achieve ultra-high light absorption rate in the full solar spectrum and keep high-efficiency seawater desalination efficiency by using an interface photo-thermal conversion technology, and meanwhile, due to the ultra-hydrophilicity, the high porosity and the large pore diameter of the material, the material can keep an excellent self-cleaning function in the evaporation process. The porous ceramic material also has good thermal stability and chemical stability, can keep high-efficiency evaporation rate under harsh conditions and achieve the effect of purifying organic solution and heavy metal ion solution.
Background
With the acceleration of global industrialization process, the dramatic increase of population and water resource pollution, the problem of shortage of fresh water resources is becoming more serious. Solar energy has the characteristics of inexhaustibility and ecological friendliness, and the development of a seawater desalination technology by utilizing solar energy and abundant seawater resources becomes an important development direction for solving the global crisis of freshwater resources. However, conventional solar desalination techniques result in lower evaporation efficiency (30-50%) due to direct contact of the light absorber material with the water body. Therefore, the interfacial solar steam reforming technology is one of important means for greatly improving the steam conversion efficiency.
The porous material provides favorable conditions for the rapid escape of steam in the seawater evaporation process due to the higher porosity and the three-dimensional communicated pore channels, thereby laying a foundation for the high seawater evaporation rate. Chinese patent application No. 202010031501.1 discloses a method for preparing hydrophobic porous wollastonite ceramic membrane for desalination by tape casting using high-silicon high-calcium industrial solid waste as raw material. The method takes high-silicon high-calcium solid waste as a raw material, and takes activated high-silicon high-calcium solid waste and activated calcium oxide and silicon dioxide as raw materials, wherein the raw materials are as follows: SiO2 2 : the solid waste is 13.6%: 35%: 51.4 percent (mass fraction), and preparing wollastonite raw material. Mixing and ball-milling wollastonite raw materials, adhesive polyether sulfone (PESf), dispersant polyvinylpyrrolidone (PVP) and organic solvent N-methyl pyrrolidone (NMP), vacuum degassing, casting and phase conversion to obtain a ceramic membrane blank, calcining, and finally modifying by a hydrophobing agent to obtain the wollastonite porous ceramic membrane with uniformly distributed pore structures, good hydrophobicity, desalination rate and desalination flux. Patent application No.: 201811139989.9 discloses a self-floating flexible carbon-based photothermal conversion film and a preparation method and application thereof, the method comprises the steps of mixing a carbon-based material, a film substrate and polyvinylpyrrolidone to obtain mixed powder, dissolving the mixed powder in an organic solvent to obtain a casting film liquid, and performing spin coating or blade coating on a panel to obtain the porous photothermal conversion film. The porous photothermal membrane for seawater desalination provided by the invention is difficult to stably operate under long-term illumination due to the organic solvent. Chinese patent application No.: 201410044511.3A porous ceramic for desalinating seawater is prepared from alumina and clay, silica through adding air bubble forming material, high-temp calcining to obtain continuous porous ceramic material, and mixing it with activated carbon to obtain filter materialThe salt content in the seawater is reduced, so that the drinking water with high quality and low cost is obtained. However, the active carbon is matched on the surface of the carrier, so that the binding force is poor, the active carbon is easy to fall off after a long time, and the active carbon does not have good circulation stability. Chinese patent application No. 971044821 discloses a method for preparing an ultrafiltration silicon dioxide film for seawater desalination, which takes porous ceramic as a carrier, takes methyl silicate or ethyl silicate as a raw material to prepare SiO2 sol, and dissolves the carrier in SiO2 sol to obtain the SiO2 film. The technology adopts toxic methyl silicate or ethyl silicate in the preparation process, is not beneficial to ecological friendliness and cannot be applied industrially.
The invention can make the light absorption material absorb sunlight efficiently and obtain higher steam conversion efficiency through selection and design of the light absorption material. However, in the practical application process, along with the evaporation of sea water, the salinity on two-dimensional light and heat material surface continues to accumulate, and these salinity accumulations make steam channel block up, not only cause evaporation efficiency's reduction still to make two-dimensional light and heat material receive destruction and can not reach long-term, high-efficient, steady operation's effect. Meanwhile, the process is complicated due to the hydrophobic modification of the photo-thermal material, for example, patent No. 201910804891.9 applied and issued by the applicant discloses a multi-stage photo-thermal seawater desalination material, and a preparation method and application thereof, wherein the self-cleaning effect is achieved by performing hydrophobic modification on the material, but the preparation process of the material is complex, and the cost is increased. Therefore, the construction of a three-dimensional porous light absorber material having a self-cleaning function by its own structural advantages has become one of important development directions for further improving the interfacial photothermal conversion efficiency and enabling the photothermal evaporator to operate stably for a long time.
Disclosure of Invention
In order to improve the self-cleaning function and the photothermal conversion efficiency of the porous ceramic material and reduce the synthesis cost, the invention provides the multistage heterogeneous porous ceramic membrane with high seawater desalination efficiency and the self-cleaning function.
The invention also provides a preparation method and application of the material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a multi-stage heterogeneous porous ceramic membrane with high seawater desalination efficiency and self-cleaning function is characterized in that the multi-stage heterogeneous porous ceramic membrane is formed by TiB 2 +Ti(C,N)+Ti 3 Two-dimensional nano photothermal materials grow in or on the porous ceramic support pore structure of the SiC, or/and carbon nano materials are deposited on the surface of the porous ceramic support pore structure; the multi-stage heterogeneous porous ceramic membrane has a three-dimensional communicated multi-stage porous structure with three pore diameters of within 10 microns, 20-80 microns and 100-800 microns simultaneously through the self reaction of raw materials and the formation of an additional pore-forming agent.
Further, the carbon nano-material is Carbon Nanotubes (CNTs) or Graphene Oxide (GO).
The method for preparing the porous ceramic membrane comprises the following steps: it is prepared from Ti and B 4 C、C 3 N 4 SiC powder as raw material, NH 4 HCO 3 Preparing a porous ceramic support body by using a method of laser ignition to generate self-propagating reaction for a pore-forming agent and an N source, wherein the reaction is as follows: ti + B 4 C+C 3 N 4 +SiC+NH 4 HCO 3 →TiB 2 +Ti(C,N)+Ti 3 SiC 2 . The porosity of the porous ceramic is up to 72%, and the pore size distribution is within 10 μm, 20-80 μm, 100-800 μm. Subsequently, two-dimensional nano photothermal materials such as transition metal sulfides, including MoS, are grown in or on the porous ceramic pore structure 2 、WS 2 And/or depositing carbon nano-materials-Carbon Nanotubes (CNTs) or Graphene Oxide (GO) on the surface of the porous material by a CVD method. The carbon nano material is used as a light absorption material, so that the light absorption rate of the heterostructure is further improved, and the photo-thermal seawater desalination efficiency is improved.
The method for preparing the porous ceramic membrane comprises the following steps:
the first step is as follows: preparation of porous ceramic Material
Weighing Ti and B according to the proportion 4 C、C 3 N 4 SiC and NH 4 HCO 3 Powder, the powder molar ratio is: ti: B 4 C:C 3 N 4 :SiC＝3:1:1:1，NH 4 HCO 3 The powder accounts for 15% of the total system by volume, and mixingMixing the powder, pressing to shape, and heating to remove NH 4 HCO 3 Thereby forming large pores in the green body;
the particle size of Ti is 200-300 meshes, B 4 The particle size of C is 5 μm, C 3 N 4 And SiC particle size 1600-3000 mesh, NH 4 HCO 3 The granularity is 500-1000 meshes;
the second step is that: synthesis of porous ceramic material
Starting a power supply of laser cladding equipment, setting the laser power to be 800W, then igniting the blank at the center of the surface of the blank by using a laser beam to enable the mixed powder blank to react, obtaining a porous ceramic material after the reaction, and using Ar gas as a protective gas in the reaction process; the main component phase of the porous ceramic material is TiB 2 +Ti(C,N)+Ti 3 SiC 2 Wherein Ti (C) , N) is a light-absorbing material having a plasmon resonance effect, TiB 2 +Ti 3 SiC 2 The porous material is reinforced; the reaction formula is as follows:
Ti+B 4 C+C 3 N 4 +SiC→TiB 2 +Ti(C,N)+Ti 3 SiC 2 ；
the third step: preparing a heterostructure by adopting a method one or/and a method two
The method comprises the following steps: thiourea and sodium molybdate are taken as precursors to be agglomerated into nano spherical MoS on the surface of the porous ceramic in a hydrothermal mode 2 And internally growing lamellar MoS 2 The hydrothermal temperature is 200 ℃, and the hydrothermal time is 24 hours; or preparing WS by ball milling calcination 2 And spraying the powder on the surface of the porous ceramic; WS 2 The preparation method comprises the following steps: taking tungsten oxide and sulfur as raw materials, and oxidizing the tungsten: mixing sulfur at a ratio of 1:3, ball milling for 24 hr, calcining the ball milled product in a tube furnace at 600 deg.C for 24 hr to obtain WS 2 Then WS 2 And spraying the powder on the surface of the porous ceramic;
the second method comprises the following steps: preparing Carbon Nanotubes (CNTs) on the surface of porous ceramic by a vapor deposition process, wherein the experimental conditions are as follows: taking nitrogen as protective gas, the atmosphere temperature is 900 ℃, acetonitrile and ferrocene are taken as a carbon source and a catalyst, and the heat preservation time is 40 minutes; or preparing Graphene Oxide (GO) on the surface of the porous ceramic by a vapor deposition process, and keeping the temperature for 20 minutes at the growth temperature of 1000 ℃ by taking methane as a carbon source under the atmosphere condition of mixing argon and hydrogen.
The multistage heterogeneous porous ceramic membrane is mainly applied to the aspect of interface photothermal seawater desalination, and the using method comprises the following steps: the photothermal seawater desalination material is combined with polyethylene foam and cotton to prepare a photothermal evaporator, wherein the polyethylene foam is used as a heat insulator to reduce heat conduction loss in the evaporation process, the cotton is used as a transmission channel of seawater, then the photothermal porous ceramic material is placed in a polytetrafluoroethylene container filled with seawater, the polytetrafluoroethylene container is placed on a balance, a simulated light source is used for irradiating, the mass change at different moments is recorded, the evaporation rate of the seawater is calculated, and further the photothermal conversion efficiency is obtained.
The invention has the advantages that:
1, inventive reactant B 4 C、C 3 N 4 The decomposition of SiC in the reaction process can obtain pores within 10 μm, the melt flow of Ti in the reaction process can form pores of 20-80 μm, and the pore-forming agent NH 4 HCO 3 The decomposition can obtain macropores with the thickness of 100-800 mu m, and three-dimensional communicated multi-stage porous ceramic materials are formed by different pore-forming mechanisms. Due to the porous structure and the large surface roughness, the material has super-hydrophilicity, and the characteristic of large aperture of the material is combined, so that salt in the evaporation process can be prevented from accumulating along with the up-and-down convection of water in the pore channel, and the natural self-cleaning advantage is exerted.
2. The porous skeleton composition of the porous ceramic material is TiB 2 +Ti(C,N)+Ti 3 SiC 2 The phase not only can resist corrosion under severe conditions, such as strong acid, strong base and the like, but also can keep the structure and the property stable without decomposition at higher temperature. Therefore, the multi-stage heterogeneous porous ceramic material has excellent chemical stability and thermal stability.
3, the multi-stage heterogeneous porous ceramic can enable an incident light path to generate diffuse reflection reaction due to a three-dimensional structure so as to improve light absorption rate, and meanwhile, the two-dimensional photothermal material with narrow band gap energy and plasma resonance effect on the surface and inside can be used for further improving the light absorption rate of the material, so that the photothermal conversion efficiency is improved. And the three-dimensional communicated pore structure of the porous ceramic material provides an excellent channel for steam to escape, and further contributes to improving the photo-thermal evaporation efficiency.
4. The porosity of the multi-stage heterogeneous porous ceramic reaches 72 percent, the sunlight absorption rate reaches 96 percent in a full spectrum range, and the water evaporation rate reaches 2.81 kg.m -2 ·h -1 Approximately 6.5 times that of pure seawater, the photothermal conversion efficiency exceeds 100%.
5. The raw materials selected in the whole process are nontoxic and harmless, so that the environment is not polluted and the human body is not injured; the whole process requirement is simple, so the porous ceramic material prepared by the invention has the advantages of low price, environmental protection, convenient industrialization, practical value and large-scale application.
Drawings
FIG. 1 shows a porous ceramic material TiB of the present invention 2 -Ti(C,N)-Ti 3 SiC 2 Schematic representation.
FIG. 2 shows a porous ceramic material TiB of the present invention 2 -Ti(C,N)-Ti 3 SiC 2 XRD diffractogram of.
FIGS. 3a-b and 3c-d are respectively multi-stage heterogeneous porous ceramic membrane TiB of the present invention 2 -Ti(C,N)-Ti 3 SiC 2 /MoS 2 SEM images of the surface (100 μm,5 μm) and the cross section (100 μm,20 μm).
FIG. 4 shows a multi-stage heterogeneous porous ceramic membrane TiB according to the present invention 2 -Ti(C,N)-Ti 3 SiC 2 /MoS 2 And porous ceramic material TiB 2 -Ti(C,N)-Ti 3 SiC 2 (ii) a diffuse reflected light absorption spectrum in the full spectral range.
FIG. 5 shows a multi-stage heterogeneous porous ceramic membrane TiB according to the present invention 2 -Ti(C,N)-Ti 3 SiC 2 /MoS 2 And porous ceramic material TiB 2 -Ti(C,N)-Ti 3 SiC 2 Mass loss curve at one sun intensity.
FIG. 6 shows a multi-stage heterogeneous porous ceramic membrane Ti according to the present inventionB 2 -Ti(C,N)-Ti 3 SiC 2 /MoS 2 Cycle test curve of (1).
FIGS. 7a and 7b are schematic diagrams of a multi-stage heterogeneous porous ceramic membrane TiB according to the present invention 2 -Ti(C,N)-Ti 3 SiC 2 /MoS 2 A real map of the self-cleaning performance and a contact angle map.
Detailed Description
The technical scheme of the invention is further explained by combining the specific embodiment according to the attached drawings.
Example one
The first step is as follows: powder preparation
Ti (200-300 mesh), B 4 C(5μm)、C 3 N 4 And SiC (1600- 4 HCO 3 (500-1000 mesh) powder is used as raw material, and the powder molar ratio is as follows: b is Ti 4 C:C 3 N 4 :SiC＝3:1:1:1，NH 4 HCO 3 The volume fraction of the powder is 15 percent of the total system volume, and the mixed powder is put into a three-dimensional mixer to be mixed for 8 hours;
the second step is that: compression molding
Compacting the mixed powder with a cylindrical die with a diameter of 2 cm under 100MPa for 5 min, heating to remove NH 4 HCO 3 And forming large pores in the green body.
The third step: synthesis of porous ceramic material
And (3) starting a power supply of laser cladding equipment, setting the laser power to be 800W, and then igniting the blank body at the center of the surface of the blank body by using a laser beam to react the mixed powder blank body to obtain the porous ceramic material shown in the figure 1. Ar gas is used as protective gas in the reaction process. The main component phase of the photothermal porous ceramic material is TiB shown in figure 2 2 +Ti(C,N)+Ti 3 SiC 2 Wherein Ti (C) , N) is a light absorbing material having a plasmon resonance effect. TiB 2 +Ti 3 SiC 2 Plays a role in reinforcing the porous material. The reaction formula is as follows:
Ti+B 4 C+C 3 N 4 +SiC→TiB 2 +Ti(C,N)+Ti 3 SiC 2 ；
the fourth step: preparation of heterostructures
MoS grows on the surface and in the interior of porous ceramic in a hydrothermal mode by taking thiourea and sodium molybdate as precursors 2 The hydrothermal temperature is 200 ℃ and the hydrothermal time is 24 h. SEM images of the prepared multi-stage heterogeneous porous ceramic membrane are shown in figures 3a-3d, and the obtained sample has a three-dimensional communicated multi-stage porous structure.
The fifth step: applications of the invention
The multistage heterogeneous porous ceramic material is combined with polyethylene foam and cotton to prepare the photothermal evaporator, wherein the polyethylene foam is used as a heat insulator to reduce heat conduction loss in the evaporation process, the cotton is used as a transmission channel of seawater, then the photothermal porous ceramic material is placed in a polytetrafluoroethylene container filled with seawater, the polytetrafluoroethylene container is placed on a balance, a simulated light source is used for irradiating, the mass change at different moments is recorded, the evaporation rate of the seawater is calculated, and further the photothermal conversion efficiency is obtained.
The porosity of the photothermal porous ceramic membrane material of example one was tested to be 72%. The solar light absorption rate is 96 percent, and the water evaporation rate is 2.81 kg.m -2 ·h -1 Approximately 6.5 times that of pure seawater, the photothermal conversion efficiency exceeds 100%. TiB 2 -Ti(C,N)-Ti 3 SiC 2 /MoS 2 And after the surface of the porous ceramic membrane is continuously illuminated for 48 hours, no salt is separated out on the surface. As can also be seen from FIG. 7a, the material can achieve a large amount of salt self-cleaning effect within 30 minutes, which proves that the material has excellent self-cleaning function.
Example two
The first step is as follows: powder preparation
Ti (200-300 mesh), B 4 C(5μm)、C 3 N 4 And SiC (1600- 4 HCO 3 (500-1000 mesh) powder is used as raw material, and the powder molar ratio is as follows: ti: B 4 C:C 3 N 4 :SiC＝3:1:1:1，NH 4 HCO 3 The volume fraction of the powder is 15 percent of the total system volume, and the mixed powder is filled into a containerMixing for 8 hours by a vitamin mixer;
the second step is that: compression molding
Compacting the mixed powder by using a cylindrical die with the diameter of 2 cm, wherein the pressure is 100MPa, the pressure maintaining time is 5 minutes, and after the compacting is finished, heating to remove the pore-forming agent to form macropores, wherein the height of the cylindrical sheet is 2 mm.
The third step: synthesis of porous ceramic material
And starting a power supply of laser cladding equipment, setting the laser power to be 800W, and then igniting the blank at the center of the surface of the blank by using a laser beam to enable the mixed powder blank to react to obtain the porous ceramic material. Ar gas is used as protective gas in the reaction process. The main component phase of the photothermal porous ceramic material is TiB 2 +Ti(C,N)+Ti 3 SiC 2 Wherein Ti (C) , N) is a light-absorbing material having a plasmon resonance effect, TiB 2 +Ti 3 SiC 2 Plays a role in enhancing the porous material, and the reaction formula is as follows:
Ti+B 4 C+C 3 N 4 +SiC+→TiB 2 +Ti(C,N)+Ti 3 SiC 2 ；
the fourth step: preparation of heterostructures
Carbon Nanotubes (CNTs) are prepared on the surface of a porous ceramic material by a vapor deposition process. The experimental conditions were: nitrogen is used as protective gas, the atmosphere temperature is 900 ℃, acetonitrile and ferrocene are used as carbon source and catalyst, and the heat preservation time is 40 minutes.
The fifth step: applications of
The multistage heterogeneous porous ceramic material is combined with polyethylene foam and cotton to prepare the photothermal evaporator, wherein the polyethylene foam is used as a heat insulator to reduce heat conduction loss in the evaporation process, the cotton is used as a transmission channel of seawater, then the photothermal porous ceramic material is placed in a polytetrafluoroethylene container filled with seawater, the polytetrafluoroethylene container is placed on a balance, a simulated light source is used for irradiating, the mass change at different moments is recorded, the evaporation rate of the seawater is calculated, and further the photothermal conversion efficiency is obtained.
Tested, example twoThe porosity of the photothermal porous ceramic membrane material was 72%. The solar light absorption rate is 95 percent, and the water evaporation rate is 2.5 kg.m -2 ·h -1 Approximately 5.7 times of pure seawater, the photothermal conversion efficiency exceeds 100%, and due to the hydrophobic property of the carbon nanotubes, the carbon nanotubes can also have good salt precipitation resistance without the hydrophobic modification step.
FIG. 4 shows the multi-stage heterogeneous porous ceramic membrane TiB of the present invention 2 -Ti(C,N)-Ti 3 SiC 2 /MoS 2 And porous ceramic material TiB 2 -Ti(C,N)-Ti 3 SiC 2 The diffuse reflection light absorption spectrum in the full spectrum range shows that the light absorption rate of the material is greatly improved after the heterostructure is prepared on the surface of the porous ceramic material.
FIG. 5 shows the multi-stage heterogeneous porous ceramic membrane TiB of the present invention 2 -Ti(C,N)-Ti 3 SiC 2 /MoS 2 And porous material TiB 2 -Ti(C,N)-Ti 3 SiC 2 The mass loss curve under the sunlight intensity shows that after the heterostructure is prepared on the surface of the porous ceramic material, the water evaporation rate of the material is greatly increased.
FIG. 6 shows a multi-stage heterogeneous porous ceramic membrane TiB according to the present invention 2 -Ti(C,N)-Ti 3 SiC 2 /MoS 2 The cycle test curve shows that the material can maintain stable high evaporation rate under continuous illumination and has excellent cycle stability.
Fig. 7a and 7b are a real figure and a contact angle diagram of an experiment on the self-cleaning function of the material, respectively, and it can be seen from fig. 7a that the salt accumulated on the surface of the material can completely disappear within 35 minutes of standing, indicating that the material has an excellent self-cleaning function, and it can be seen from the contact angle diagram of fig. 7b that the material has super-hydrophilicity.
The above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (3)
1. A porous ceramic membrane with high seawater desalination efficiency and self-cleaning function is characterized in that the porous ceramic membrane is formed by TiB in phase composition 2 +Ti(C,N )+Ti 3 SiC 2 Two-dimensional nano photothermal materials grow in or on the porous ceramic support pore structure, or carbon nano materials are deposited on the surface of the porous ceramic support pore structure, and the porous ceramic membrane is a multi-stage heterogeneous porous ceramic membrane; the multi-stage heterogeneous porous ceramic membrane is a three-dimensional communicated multi-stage porous structure which has three apertures of less than 10 mu m, 20-80 mu m and 100-800 mu m simultaneously through the self reaction of raw materials and the formation of an added pore-forming agent; the porous ceramic film is formed by Ti and B 4 C、C 3 N 4 SiC powder as raw material, NH 4 HCO 3 Preparing a porous ceramic support body by using a method of laser ignition to generate self-propagating reaction for a pore-forming agent and an N source, wherein the reaction is as follows: ti + B 4 C + C 3 N 4 + SiC+NH 4 HCO 3 →TiB 2 +Ti(C,N ) + Ti 3 SiC 2 (ii) a And then growing a transition metal sulfide two-dimensional nano photothermal material in or on the surface of the porous ceramic support pore structure, or depositing carbon nano tubes or graphene oxide on the surface of the porous ceramic support pore structure by a vapor deposition method.
2. The method for preparing a porous ceramic membrane having high seawater desalination efficiency and self-cleaning function as claimed in claim 1, comprising the steps of:
the first step is as follows: preparation of porous ceramic support Material
Weighing Ti and B according to the proportion 4 C、 C 3 N 4 SiC and NH 4 HCO 3 Powder, the powder molar ratio is: b is Ti 4 C: C 3 N 4 : SiC =3: 1: 1: 1，NH 4 HCO 3 Powder of Ti and B 4 C、 C 3 N 4 SiC and NH 4 HCO 3 The volume fraction of the total system of the five powders is 15 percent, the mixed powder is evenly mixed and pressed into a compact for forming, and then NH is removed by heating 4 HCO 3 FromForming large pores in the green body;
the particle size of the Ti is 200-300 meshes, B 4 The C particle size is 5 mu m, C 3 N 4 And SiC particle size 1600-3000 mesh, NH 4 HCO 3 The granularity is 500-1000 meshes;
the second step is that: porous ceramic support synthesis
Starting a power supply of laser cladding equipment, setting the laser power to be 800W, then igniting the blank at the center of the surface of the blank by using a laser beam to react the mixed powder blank to obtain a porous ceramic support body after the reaction, wherein Ar gas is used as protective gas in the reaction process; the main component phase of the porous ceramic support body is TiB 2 +Ti(C,N )+Ti 3 SiC 2 Wherein Ti (C, N) is a light absorbing material with plasmon resonance effect, TiB 2 +Ti 3 SiC 2 The porous material is reinforced; the reaction formula is as follows:
Ti+B 4 C+C 3 N 4 +SiC→TiB 2 +Ti(C,N )+Ti 3 SiC 2 ；
the third step: preparing a heterostructure by adopting the first method or the second method
The method comprises the following steps: thiourea and sodium molybdate are taken as precursors to be agglomerated into nano spherical MoS on the surface of a porous ceramic support body in a hydrothermal mode 2 And growing the lamellar MoS inside the porous ceramic support 2 The hydrothermal temperature is 200 ℃, and the hydrothermal time is 24 hours; or preparing WS by ball milling calcination 2 And WS 2 Spray-coating on the surface of a porous ceramic support, WS 2 The preparation method comprises the following steps: taking tungsten oxide and sulfur as raw materials, and oxidizing the tungsten: mixing sulfur =1:3, ball milling for 24h, calcining the ball milled product in a tube furnace at 600 ℃ for 24h to obtain WS 2 ；
The second method comprises the following steps: preparing carbon nanotubes on the surface of the porous ceramic support body by a vapor deposition process, wherein the experimental conditions are as follows: taking nitrogen as protective gas, the atmosphere temperature is 900 ℃, acetonitrile as a carbon source, ferrocene as a catalyst, and the heat preservation time is 40 minutes; or preparing graphene oxide on the surface of the porous ceramic support body by a vapor deposition process, and keeping the temperature for 20 minutes at the growth temperature of 1000 ℃ by taking methane as a carbon source under the atmosphere condition of mixing argon and hydrogen.
3. The method of claim 1, wherein the porous ceramic membrane is combined with polyethylene foam and cotton to form a photothermal evaporator, wherein the polyethylene foam is used as a thermal insulator to reduce the heat conduction loss during evaporation, and the cotton is used as a transport channel for seawater; and then placing the photo-thermal evaporator in a polytetrafluoroethylene container filled with seawater, placing the polytetrafluoroethylene container on a balance, irradiating by using a simulated light source, recording mass changes at different moments, and calculating the evaporation rate of the seawater so as to obtain the photo-thermal conversion efficiency.
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